Sulfonated n-substituted amino-anthraquinones



Patented Nov. 4, 1952' UNITED STATES PATENT o/Er ci: g g 2,616,900 7 QsULFonA'rEn N-SUBSTITUTED AMINO v ANTHRAQUINO NES "Samuel von Allmen andHans Eggenberger, Basel, Switzerland, assignors to Sandoz A. (3., Ease],I Switzerland, a Swiss firm No:Drawing. Application May'23. 1949,SeriallVo.

' 94,936. In Switzerland May 27, 1948 The present invention relates toblue vivid dyestuffs of theanthraqui-none series and to a process for hm Ie W Q.

U. S. Patent No. 1,821,043

discloses dyestuffs of the general form l J dyestuffs, however,possessnolevelling properties.

It has been found t a. le dyestuffs Ipossessing g'oo'd levellingproperties can be obtained if the anthraquinone derivatives of thegeneral formula wherein R is hydrogen or alkyl and a: and y are hydrogenor halogen, and wherein in the hydroaromatic radical one hydrogen atomis substituted by an aryl or aralkyl radical or two adjacent hydrogenatoms are parts of a benzene nucleus, are treated with sulphonatingagents.

The new products are polysulphonic acids and differ from themonosulphonated dyestuffs of the above formula principally by the factthat they dye animal fibres such as wool, silk, etc. and artificialfibres such for example as nylon only in a sulphuric acid bath withequally good properties. This makes them suitable for the dyeing ofwool, felt and similar fabrics. The sulfonation may be carried out in aknown manner by dissolving the anthraquinone derivative at roomtemperature in concentrated sulphuric acid, sulphuric acid monohydrate,or halogen-sulphonic acid, whilst cooling by means of ice or water,allowing it to digest for some time and, if necessary, adding oleumuntil a sample tested in cold water is readily soluble therein. Afterpouring onto ice or into a salt solution the dyestuff will be isolatedin the conventional manner, purified and worked up.

The dyestuffs thus produced dissolve readily in cold water.

" 'i'xarlipleil Q,

5 parts of l-ami nol-(lf g2':3":4'-tetrahydro- 2' naphthylamino)anthraquinone 2 sulphonic acid are introduced into 25 parts of sulphuricacid monohydrate with stirring andice cooling. After a period of onehour the dyestufi has become considerably moresoluble and is worked up.The fibrewill take the vivid blue dyestufi properly only when applied ina sulphuric acid bath. 'Dissolvedin concentrated sulphuric acid thecolor of the dyestuffis faintly greenish and the addition of a littleparaformaldehyde causes it to turn-greenish blue If the'su'lphonation iscarried out at a'higher temperature or with diluted oleum a still'm'oresoluble product is obtained. I r raampzezg If in Example 1 the l-aminol-(lj":2':3:4'- tetrahydro 2 naphthylamino)"--"anthraquinone-2-su1phoniacid is replaced by 1-amin0-4- (1:2':3:4.' -.-tetrahyd ro 2naphthylamino)- 6:7-dichlor-anthraquinone-2-sulphonic acid, a dyestuffof a somewhatgreener shade is obtained.

Similar dyestuifs are obtained if l-aminol- (1":2':3:4' tetrahydro 2'naphthylamino)- 6:'7-dich1oranthraquinone-2-sulphonic acid is replacedby l-amino-4-(1 :2 :3 :4'-tetrahydro-2- naphthylaminoor-4'-phenylhexahydroanilido) -6- or -7-chloror -bromanthraquinone-2-sulphonic acid.

Example 3 10 parts of l-amino-l-(4-phenylhexahydroanilido)-anthraquinone2-sulphonic acid are dis- Example 4 6 parts of1-amino-4-(1z2'z3':4'-tetrahydro- 1' naphthylamino) anthraquinone 2sulphonic acid are monosulphonated in 30 parts of 3 sulphuric acidmonohydrate by means of ice cooling. The disulphonated dyestuff is veryreadily soluble in water and is taken on by the fibre only in asulphuric acid bath.

Example 5 5 parts of 1-amino-4 (4-phenyl-hexahydroanilido)-anthraquinone-2-sulphonic acid are introduced into 25 parts ofsulphuric acid monohydrate while stirring and cooling by means of water.Then parts of 28% oleum are added. After half an hour the dyestufi hasbecome considerably more soluble and is workedup. The

fibre will take the vivid blue dyestufif'only in a sulphuric acid bath.Dissolved in concentrated sulphuric acid the color is faintly greenishand the addition of a little paraformaldehyde causes it to turngreenish-blue.

Instead of 28% oleum chlorosulphonicacid can also be used assulphonating agent.

What we claim is:" I

1. An acid anthraquinone dyestufl? corresponding to the formula H Oak 73. The anthraquinone dyestufi of the formula SOzH 4. The anthraquinonedyestufi of the formula SAMUEL voN ALLMEN.

HANS EGGENBERGER.

REFERENCES CITED 1 The following references are of record in the file ofthis patent:

UNITED STATES PATENTS Number Number Name Date Weinand Sept. 1, 1931Buckley et al Aug. 26, 1947 FOREIGN PATENTS Country Date Great BritainAug. 26, 1931 Great Britain Oct. 3, 1932

1. AN ACID ANTHRAQUINONE DYESTUFF CORRESPONDING TO THE FORMULA